C(H)Cl=C(H)CF3



































 









Chlorine


Nuclear Quadrupole Coupling Constants


in 1-Chloro-3,3,3-trifluoropropene


 








 








 








Calculation of the chlorine nqcc tensors in both E and Z conformers of 1-chloro-3,3,3-trifluoropropene was made on a ropt and ~re molecular structures, where ropt is given by MP2/aug-cc-pVTZ(G03) optimization and ~re is ropt but with empirically corrected CCl, C-C, C=C, and CF bond lengths.   Calculated nqcc's are compared with the experimental results of Marshall et al. [1] in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.

 


































E Conformer


Z Conformer





















In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  (degrees) is the angle between its subscripted parameters.


RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation for the B1LYP/TZV(3df,2p) model for calculation of the chlorine efg's/nqcc's. 

 








 








 
   








Table 1.  Chlorine nqcc's in E-1-Chloro-3,3,3-trifluoropropene (MHz).  Calculation was made on ropt and ~re molecular strcutures.
   










Calc ropt
Calc ~re
Expt. [1]
   







Xaa (35Cl) - 63.35 -
63.12
-
63.153(15)


Xbb
32.88

32.77

31.695(19)


Xcc
30.47
30.35

31.458(20)


|Xab|
30.96
30.88




 







RMS
0.90 (2.1 %)

0.89 (2.1 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
41.99
41.86




Xyy
30.47
30.35



Xzz - 72.46 -
72.21




ETA - 0.159 -
0.159




z,a
16.38
16.39




a,CCl
16.34

16.31




z,CCl
  0.04

  0.08




 







Xaa (37Cl) -
49.99
-
49.80
-
49.830(27)


Xbb
25.97

25.88

24.795(40)


Xcc
24.01

23.92

25.035(40)


|Xab|
24.32

24.25

13.0(12)











RMS

0.90 (2.7 %)

0.90 (2.7 %)



RSD

0.44 (1.1 %)
0.44 (1.1 %)













 








 








   








Table 2.  Chlorine nqcc's in Z-1-Chloro-3,3,3-trifluoropropene (MHz).  Calculation was made on ropt and ~re molecular strcutures.
   










Calc ropt
Calc ~re
Expt. [1]
   







Xaa (35Cl)
  9.38

  9.46

  8.7789(27)


Xbb -
38.84
-
38.80
-
39.1803(26)


Xcc
29.46
29.33

30.4013(25)


|Xab|
52.62
52.39

51.937(38)


 







RMS
0.67 (2.6 %)

0.71 (2.7 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
43.15
43.01




Xyy
29.46
29.33



Xzz - 72.61 -
72.34




ETA - 0.188 -
0.189




z,a
122.69
122.63




a,CCl
121.93

121.88




z,CCl
    0.76

    0.75




 







Xaa (37Cl)
  6.96

  7.03




Xbb -
30.18
-
30.15




Xcc
23.22

23.12




|Xab|
41.66

41.48













RMS








RSD

0.44 (1.1 %)
0.44 (1.1 %)













 








 












Table 3.  1-Chloro-3,3,3-trifluoropropene:  Structure parameters, ropt and ~re  ( and degrees).  Approximate equilibrium bond lengths (~re) are given in parentheses.




  E-Conformer







 H
 C,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 Cl,2,B4,1,A3,3,D2,0
 H,3,B5,2,A4,1,D3,0
 F,4,B6,3,A5,2,D4,0
 F,4,B7,3,A6,2,D5,0
 F,4,B8,3,A7,2,D6,0
      Variables:
 B1=1.07896336
 B2=1.33019027              (1.3265)
 B3=1.48920885              (1.4886)
 B4=1.71692352              (1.7137)
 B5=1.07998763
 B6=1.34107028              (1.3350)
 B7=1.34528019              (1.3391)
 B8=1.34528019              (1.3391)
 A1=123.08360685
 A2=121.33080695
 A3=114.55482814
 A4=122.46470842
 A5=112.90888254
 A6=111.03518913
 A7=111.03518913
 D1=0.
 D2=180.
 D3=180.
 D4=0.
 D5=120.69175362
 D6=-120.69175362





Z-Conformer






 Cl
 C,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 H,2,B4,1,A3,3,D2,0
 H,3,B5,2,A4,1,D3,0
 F,4,B6,3,A5,2,D4,0
 F,4,B7,3,A6,2,D5,0
 F,4,B8,3,A7,2,D6,0
      Variables:
 B1=1.71412064              (1.7109)
 B2=1.33277913              (1.3290)
 B3=1.49505008              (1.4942)
 B4=1.0794954
 B5=1.07978201
 B6=1.34385397              (1.3377)
 B7=1.34258892              (1.3365)
 B8=1.34258892              (1.3365)
 A1=124.62053912
 A2=124.85655649
 A3=114.02963855
 A4=118.86768877
 A5=109.9234784
 A6=112.49058628
 A7=112.49058628
 D1=0.
 D2=180.
 D3=180.
 D4=180.
 D5=-60.5547442
 D6=60.5547442








 













Table 4.  1-Chloro-3,3,3-trifluoropropene:  Rotational Constants (MHz).  35Cl species.
 





 ropt  ~re    Expt. [1]





E Conformer
A 5293. 5338.
5300.21(72)

B   949.   953.
  947.86424(50)

C   937.   941.
  935.98703(50)





Z Conformer
A
4389.
4417.
4387.26876(19)

B
1384.
1391.
1831.692240(71)

C
1291.
1297.
1288.392056(70)


 








 








[1] M.D.Marshall, H.O.Leung, M.A.Wronkovich, M.E.Tracy, L.Hoque, A.M.Randy-Cofie, and  A.K.Dao, Abstract TC07, 72nd ISMS, Champaign-Urbana, Illinois, 2017.


 








 








2-Chloropropene
2-Chloro-3,3,3-trifluoropropene


 








 








Table of Contents




Molecules/Chlorine




 








 













1ClCF3Propene.html






Last Modified 20 Aug 2017